eprintid: 9715 rev_number: 4 userid: 6 dir: disk0/00/00/97/15 datestamp: 2011-11-10 20:05:18 lastmod: 2016-11-15 13:51:46 status_changed: 2011-11-10 20:05:18 type: thesis_degree metadata_visibility: show contact_email: jup19@pitt.edu item_issues_count: 0 eprint_status: archive creators_name: Park, Jung-hyun creators_email: jup19@pitt.edu creators_id: JUP19 title: STUDIES ON AZA-CYCLOADDITION:PART 1. INTRAMOLECULAR KETENE-IMINE CYCLOADDITIONPART 2. IMINIUM ION-MEDIATED [4+2] CYCLOADDITION ispublished: unpub divisions: sch_as_chemistry full_text_status: public keywords: Diels-Alder; imine; ketene abstract: Part 1. Intramolecular Ketene-Imine CycloadditionThe ketene-imine cycloaddition reactions, developed previously by the Nelson group, have beenextended to the intramolecular cycloaddition of the ketene-imine cycloaddition. Initial resultsshowed that the intramolecular cycloaddition exhibited excellent enantioselectivity, but it wassuffered from poor diastereoselectivity. Later, it was shown that proper functionality on thetether of the substrate could improve diastereoselectivity.Part 2. Iminium Ion-Mediated [4+2] CycloadditionThe N-alkenyl iminium ion cycloaddition reaction (AIC reaction), developed previously by theNelson group, was further investigated for the more detailed understaniding. As a result, tworeaction pathways (Diels-Alder pathway and oxo-Diels-Alder pathway) of the AIC reaction werefound when carbamate-protected N-alkenyl iminium ion was employed as a 4Ĉ-electroncomponent. Based on this observation, efficient methods to turn off either one of the tworeaction pathways were proposed. date: 2011-01-31 date_type: completed institution: University of Pittsburgh refereed: TRUE etdcommittee_type: committee_chair etdcommittee_type: committee_member etdcommittee_type: committee_member etdcommittee_type: committee_member etdcommittee_name: Nelson, Scott G etdcommittee_name: Doemling, Alexander etdcommittee_name: Wilcox, Craig S etdcommittee_name: Cohen, Theodore etdcommittee_email: sgnelson@pitt.edu etdcommittee_email: asd30@pitt.edu etdcommittee_email: daylite@pitt.edu etdcommittee_email: cohen@pitt.edu etdcommittee_id: SGNELSON etdcommittee_id: ASD30 etdcommittee_id: DAYLITE etdcommittee_id: COHEN etd_defense_date: 2011-08-27 etd_approval_date: 2011-01-31 etd_submission_date: 2010-11-18 etd_access_restriction: immediate etd_patent_pending: FALSE assigned_doi: doi:10.5195/pitt.etd.2011.9715 thesis_type: dissertation degree: PhD committee: Scott G. Nelson (sgnelson@pitt.edu) - Committee Chair committee: Alexander Doemling (asd30@pitt.edu) - Committee Member committee: Craig S. Wilcox (daylite@pitt.edu) - Committee Member committee: Theodore Cohen (cohen@pitt.edu) - Committee Member etdurn: etd-11182010-170358 other_id: http://etd.library.pitt.edu/ETD/available/etd-11182010-170358/ other_id: etd-11182010-170358 citation: Park, Jung-hyun (2011) STUDIES ON AZA-CYCLOADDITION:PART 1. INTRAMOLECULAR KETENE-IMINE CYCLOADDITIONPART 2. IMINIUM ION-MEDIATED [4+2] CYCLOADDITION. Doctoral Dissertation, University of Pittsburgh. (Unpublished) document_url: http://d-scholarship-dev.library.pitt.edu/9715/1/Park_27Aug2010_1.pdf